EP2652075A2 - Körperpflegezusammensetzungen mit wässrigen zusammensetzungen viskoelastischer tenside und hydrophob modifizierten polymeren - Google Patents

Körperpflegezusammensetzungen mit wässrigen zusammensetzungen viskoelastischer tenside und hydrophob modifizierten polymeren

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Publication number
EP2652075A2
EP2652075A2 EP11801695.5A EP11801695A EP2652075A2 EP 2652075 A2 EP2652075 A2 EP 2652075A2 EP 11801695 A EP11801695 A EP 11801695A EP 2652075 A2 EP2652075 A2 EP 2652075A2
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EP
European Patent Office
Prior art keywords
personal care
care composition
polymer
monomer
carbon atoms
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP11801695.5A
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English (en)
French (fr)
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EP2652075B1 (de
Inventor
Qingwen Wendy Yuan-Huffman
Klin A. Rodrigues
Jian Zhou
Stuart Peter Robert Holt
Elliot Isaac Band
Samuel Anthony Vona Jr.
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Nouryon Chemicals International BV
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Akzo Nobel Chemicals International BV
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Priority to EP15168141.8A priority Critical patent/EP2940095A1/de
Priority to EP11801695.5A priority patent/EP2652075B1/de
Publication of EP2652075A2 publication Critical patent/EP2652075A2/de
Application granted granted Critical
Publication of EP2652075B1 publication Critical patent/EP2652075B1/de
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/602—Compositions for stimulating production by acting on the underground formation containing surfactants
    • C09K8/604—Polymeric surfactants
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8105—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • A61K8/8111—Homopolymers or copolymers of aliphatic olefines, e.g. polyethylene, polyisobutene; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8147—Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/87—Polyurethanes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/10—Washing or bathing preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/12—Preparations containing hair conditioners
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q9/00—Preparations for removing hair or for aiding hair removal
    • A61Q9/02—Shaving preparations
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C09K8/66—Compositions based on water or polar solvents
    • C09K8/68—Compositions based on water or polar solvents containing organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/84—Compositions based on water or polar solvents
    • C09K8/86—Compositions based on water or polar solvents containing organic compounds
    • C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/25—Methods for stimulating production
    • E21B43/26—Methods for stimulating production by forming crevices or fractures
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/30—Viscoelastic surfactants [VES]
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/92—Sulfobetaines ; Sulfitobetaines

Definitions

  • the present invention relates to personal care compositions comprising aqueous viscoelastic compositions comprising at least one viscoelastic surfactant, and at least one hydrophobically modified polymer.
  • WO 2003/056130 proposes an improvement on such existing systems and proposes to use a combination of viscoelastic surfactants and a hydrophobically modified polymer, wherein the concentration of the hydrophobically modified polymer is comprised between its overlap concentration c * and its entanglement concentration c e .
  • the viscoelastic fluids of WO 2003/056130 have certain commercial value, they contain high amounts of both surfactant and hydrophobically modified polymer in order to achieve aqueous compositions with the desired viscosity.
  • the hydrophobes are connected to the polymer backbone via a degradable group.
  • the high molecular weight polymers are difficult to dissolve and difficult to distribute homogeneously in aqueous formulations.
  • Personal cleansing products such as shampoos, liquid hand soaps and body washes, not only must be able to clean the desired surfaces of the body, but they should also be aesthetically pleasing throughout all aspects of the consumer experience. For example, it is desirable that such cleansers should also provide pleasing experiences when dispensing the product, applying it, creating lather, cleansing, and rinsing the product. It is desirable that liquid cleansing products to have a rich and luxurious aesthetic upon dispensing and application. Furthermore, consumers often equate a rich and luxurious lather to the cleansing efficacy of the product. Additionally, consumers have grown to expect additional benefits from their liquid cleansing products beyond cleansing. Such additional benefits include moisturization, conditioning, exfoliation, protection, and delivery of beneficial active ingredients to the hair and skin.
  • the characteristics can be improved by addition of salt.
  • Addition of salt to certain surfactant solutions induces a structural transition from spherical micelles to worm-like micelles.
  • not all surfactant systems are sensitive to addition of salt in this way.
  • a variety of other types of components can be added to the surfactant systems to achieve the desired characteristics. Examples of such components include water soluble/dispersible thickeners that effectively thicken the system and chemicals that can crystallize to form complex three dimensional structures, such as PEG150 distearate,
  • the above thickeners tend to be high molecular weight species that effectively thicken aqueous systems. Some drawbacks to these thickeners are that they can be difficult to handle due to their high viscosity, poor dissolution speed, their relatively high level usage requirement and their negatively impact the clarity. It is therefore desirable to provide chemicals that can more easily be incorporated into liquid cleansing products that enable rheological characteristics of surfactant systems, that enable suspension of benefit agents and that are consistent with the rich and luxurious aesthetic that consumers demand, while reducing the overall level of surfactant required to achieve these benefits.
  • High molecular weight polymers are generally difficult to dissolve and difficult to distribute homogeneously in aqueous formulations. Therefore, another solution is desired. More specifically, there is a need in the art for aqueous surfactant based systems with reduced amount of chemicals to obtain a certain viscosity or compositions with a higher viscosity when the same amount of chemicals are used, the amounts being based on the weight of the chemicals in the final composition, thereby further reducing the costs involved in the use of said fluid and/or expanding the applications wherein the compositions can be used. Also there is a need to be able to use polymers that are more easily dispersible in aqueous formulations.
  • the invention provides a personal care composition comprising an aqueous viscoelastic composition comprising one or more viscoelastic surfactants in combination with one or more hydrophobically-modified polymers and a personal care active ingredient.
  • Figure 1 is chart illustrating the rheology profile determined by Steady Strain Sweep test for Example 1 and comparative examples A and B.
  • Figure 2 is chart illustrating the rheology profile determined by Steady Strain Sweep test for Example 2 and comparative examples C and D.
  • Figure 3 is a chart illustrating the rheology profile determined by Steady Strain
  • Figure 4 is a chart illustrating the rheology profile determined by Steady Strain Sweep test for Example 5 and comparative examples H and I.
  • Figure 5 is a chart illustrating the rheology profile determined by Steady Strain Sweep test for Example 6 and comparative example J.
  • Figure 6 is a chart illustrating the results of steady state sweep measurements to determine zero shear viscosity.
  • Figure 7 is a chart illustrating the results of steady state sweep measurements to determine zero shear viscosity comparing fitted data to observed data.
  • Figure 8 is a chart showing the results of zero shear viscosity vs. % salt for 8 dilution experiments at various surfactant concentrations, four according to the present invention and four without the polymer-surfactant combination.
  • Figure 9 is a chart showing the results showing Elastic Modulus as a function of stress for two compositions prepared according to Examples 10 and 5, respectively.
  • the invention generally provides a personal care composition comprising an aqueous viscoelastic composition and a personal care active ingredient.
  • the viscoelastic composition comprises one or more viscoelastic surfactants in combination with one or more hydrophobically-modified polymers.
  • the viscoelastic surfactant is of the conventional type and can be selected from amine oxide surfactants including amidoamine oxide surfactants, amphoteric surfactants, zwitterionic surfactants, anionic surfactants, cationic surfactants and mixtures of two or more thereof.
  • the elastic component storage shear modulus G'
  • the viscous component that is G' ⁇ G"
  • G' the viscous component
  • G' ⁇ G at some point or over some range of points below a frequency of about 10 rad/sec, typically between about 0.001 to about 10 rad/sec, more typically between 0.1 to 10 rad/sec, at a given temperature and if G' > 10 ⁇ 2 Pascal, preferably more than 10 ⁇ 1 Pascal, the fluid is considered viscoelastic at that temperature.
  • the definition and rheological measurement of G' and G" are generally described in Barnes H. A. et al., "An Introduction to Rheology", pp.45-54, Elsevier, Amsterdam (1997).
  • the viscoelastic surfactant is of the conventional type. It is well known that viscoelastic surfactants provide viscoelasticity by forming a different type of micelle than the usual spherical micelles formed by most surfactants. Viscoelastic surfactants form elongated, often cylindrical, micelles which can be described as worm-like, thread-like, or rod-like micelles. Typically it is said that the shape and size of a micelle is a function of the molecular geometry of its surfactant molecules and solution conditions such as surfactant concentration, temperature, pH, and ionic strength. The formation of long, cylindrical micelles creates useful rheological properties.
  • Viscoelastic surfactant exhibits shear-thinning behavior, and remain stable despite repeated high shear applications. By comparison, a typical polymeric thickener will irreversibly degrade when subjected to high shear applications.
  • a viscoelastic surfactant is a surfactant that forms a visocelastic fluid in an aqueous media.
  • amine oxide surfactants contemplated for use in the present invention as viscoelastic surfactants include those of the following structural formula (I):
  • Ri is a hydrophobic moiety of alkyl, alkenyl, cycloalkyl, alkylarylalkyl, alkoxyalkyl, alkylaminoalkyl or alkylamidoalkyl. Ri has from about 8 to about 30 carbon atoms and may be straight or branched chained and saturated or unsaturated. Examples of long chain alkyl groups include, but not limited to, octadecenyl (oleyl), octadecyl (stearyl), docosenoic (erucyl) and the derivatives of tallow, coco, soy and rapeseed oils.
  • R2 and R3 are, independently, hydrogen or aliphatic group (i.e.
  • aliphatic groups include alkyl, alkenyl, cycloalkyl, alkylaryl, hydroxyalkyl, carboxyalkyl and hydroxyalkyl- polyoxyalkylene.
  • the aliphatic group can be straight or branched chained and saturated or unsaturated.
  • amidoamine oxide surfactants contemplated for use as viscoelastic surfactants in the present invention include those of the following structural formula (II): o > ⁇
  • Ri is a straight or branched chained and saturated or unsaturated aliphatic group of from about 8 to about 30 carbon atoms, preferably from about 14 to about 21 carbon atoms. More preferably, R1 is a fatty aliphatic derived from natural fats and oils having an iodine value of from about 1 to about 140, preferably from about 30 to about 90, and more preferably from 40 to about 70. Ri may be restricted to a single chain length or may be of mixed chain length such as those groups derived from natural fats and oils or petroleum stocks.
  • R 2 is a straight or branched-chained, substituted or unsubstituted, divalent alkylene group of from 2 to about 6 carbon atoms, preferably, of 2 to 4 carbon atoms and more preferably of 3 carbon atoms;
  • R 3 and R4 are the same or different and are selected from alkyl or hydroxyalkyl groups of from 1 to about 4 carbon atoms and are preferably hydroxyethyl or methyl.
  • R 3 and R4 in the amidoamine oxide of formula (II) together with the nitrogen atom to which these groups are bonded form a heterocyclic ring of up to 6 members; and R 5 is hydrogen or a Ci - C 4 alkyl or hydroxyalkyl group.
  • amidoamine oxide contemplated by the present invention include, but are not limited to, those selected from the group consisting of tallow amidoalkylamine oxide, hardened tallow amidoalkylamine oxide, rapeseed amidoalkylamine oxide, hardened rapeseed amidoalkylamine oxide, tall oil amidoalkylamine oxide, hardened
  • amidoalkylamine oxide coco amidoalkylamine oxide, stearyl amidoalkylamine oxide, oleyl amidoalkylamine oxide, soya amidoalkylamine oxide, and mixtures thereof.
  • amidoamine oxides of the present invention include, but are not limited to, the following: tallow amidopropyl dimethylamine oxide,
  • a cationic surfactant has a positively charged moiety regardless of pH.
  • cationic surfactants contemplated for use as viscoelastic surfactants in the present invention include those selected from quaternary salts, certain amines and combinations thereof.
  • the quaternary salts have the structural formula (III)
  • Ri is a hydrophobic moiety of alkyl, alkenyl, cycloalkyl, alkylarylalkyl, alkoxyalkyl, alkylaminoalkyl or alkylamidoalkyl. Ri has from about 8 to about 30 carbon atoms and may be straight or branched chained and saturated or unsaturated. Examples of long chain alkyl groups include, but are not limited to, octadecenyl (oleyl), octadecyl (stearyl), docosenoic (erucyl) and the derivatives of tallow, coco, soy and rapeseed oils;
  • R 2 , R 3 and R4 are, independently, at least partially aliphatic groups having from 1 to about 30 carbon atoms, preferably from about 1 to about 20 carbon atoms, more preferably from about 1 to about 10 carbon atoms, and most preferably from about 1 to about 6 carbon atoms.
  • Representative aliphatic groups include alkyl, alkenyl, alkylaryl, alkoxyalkyl, hydroxyalkyl, carboxyalkyl and hydroxyalkyl-polyoxyalkylene.
  • the aliphatic group can be straight or branched chained and saturated or unsaturated, and;
  • X " is a suitable counter-anion.
  • the counter-anion is typically an inorganic anion such as a sulfate such as (CH 3 ) 2 S0 4 " , a nitrate, a perchlorate or a halide such as CI " , Br , or an aromatic organic anion such as salicylate, naphthalene sulfonate, p- and m- chlorobenzoates, 3,5-, 3,4-, and 2,4-dichlorobenzoates, t-butyl and ethyl phenate, 2,6- and 2,5-dichlorophenates, 2,4,5- trichlorophenate, 2,3,5,6-tetrachlorophenate, p-methyl phenate, m-chlorophenate, 3,5,6-trichloropicolinate, 4-amino- 3,5,6-, 2,4- dichlorophenoxyacetate.
  • the amines have the following structural formula (IV)
  • the zwitterionic surfactant has a permanently positively charged moiety in the molecule regardless of pH and a negatively charged moiety at alkaline pH.
  • selected zwitterionic surfactants that are useful as viscoelastic surfactants in the present invention have the following structural formula (V):
  • Ri is hydrophobic moiety of alkyl, alkenyl, cycloalkyl, alkylarylalkyl, alkoxyalkyl, alkylaminoalkyl or alkylamidoalkyl.
  • Ri has from about 8 to about 30 carbon atoms and may be straight or branched chained and saturated or unsaturated. Examples of long chain alkyl groups include, but are not limited to, octadecenyl (oleyl), octadecyl (stearyl), docosenoic (erucyl) and the derivatives of tallow, coco, soy and rapeseed oils;
  • R 2 and R 3 are, independently, at least partially aliphatic groups having from 1 to about 30 carbon atoms, preferably from about 1 to about 20 carbon atoms, more preferably from about 1 to about 10 carbon atoms, and most preferably from about 1 to about 6 carbon atoms.
  • Representative aliphatic groups include alkyl, alkenyl, alkylaryl, alkoxyalkyl, hydroxyalkyl, carboxyalkyl and hydroxyalkyl-polyoxyalkylene.
  • the aliphatic group can be straight or branched chained and saturated or unsaturated, and;
  • Ri is a hydrocarbyl radical (e.g. alkylene) with a chain length of 1 to 4 carbon atoms. Preferred are methylene or ethylene groups. When it is zwitterionic, the surfactant is associated with both negative and positive counter-ions. Anions are typically as defined above for X " for the cationic surfactant. In an embodiment any cation is suitably elected from Na + , K + , NH4+, and amine salts, such as (CH 3 ) 2 NH 2 + . Amphoteric Viscoelastic Surfactant
  • amphoteric surfactant has both a positively charged moiety and a negatively charged moiety over a certain pH range (e.g. typically slightly acidic), only a negatively charged moiety over a certain pH range (e.g. typically slightly alkaline) and only a positively charged moiety at a different pH (e.g. typically moderately acidic).
  • amphoteric surfactants suitable for use as viscoelastic surfactants in the present invention are represented by following the structural formula (VI):
  • Ri is a hydrophobic moiety of alkyl, alkenyl, cycloalkyl, alkylarylalkyl, alkoxyalkyl, alkylaminoalkyl or alkylamidoalkyl. Ri has from about 8 to about 30 carbon atoms and may be straight or branched chained and saturated or unsaturated. Examples of long chain alkyl groups include, but are not limited to, octadecenyl (oleyl), octadecyl (stearyl), docosenoic (erucyl) and the derivatives of tallow, coco, soy and rapeseed oils;
  • R 2 has the meaning as defined above for the residue R 2 of the zwitterionic surfactant
  • R 3 is a hydrocarbyl radical (e.g. alkylene) with a chain length of 1 to 4 carbon atoms. Preferred are methylene or ethylene groups.
  • anionic surfactant has a negatively charged moiety regardless of pH.
  • anionic surfactants contemplated for use as viscoelastic surfactants in the present invention include those of the following structural formulas (VII), (VIII) and/or (Villi). ⁇ (VII)
  • R is the hydrophobic moiety of alkyl, alkenyl, cycloalkyl, alkylarylalkyl, alkoxyalkyl, alkylaminoalkyl or alkylamidoalkyl.
  • R is a saturated or unsaturated, straight or branched alkyl chain of at least 8 carbon atoms, and in another embodiment from 8 to 30 carbon atoms.
  • long alkyl chain groups include, but not limited to, octadecenyl (oleyl), lauryl, octadecyl (stearyl), docosenoic (erucyl) and the derivatives of tallow, coco, soy and rapeseed oils;
  • Z is the negatively charged hydrophilic head of the surfactant.
  • Z is suitably selected from the group consisting of carboxylate COO " , sulfonate SO 3 " , sulfate SO 4 "
  • Z may be a carboxylate group COO " or a sulfonate group SO 3 " ;
  • X is a stabilizing group.
  • X is preferably a cleavable bond.
  • X is an ester, amid, reverse ester or reverse amide group;
  • Y is a space group, which separates the cleavable group X and the hydrophilic head of the surfactant.
  • Y is preferably a linear, saturated or unsaturated hydrocarbon chain of 1 , 2 or 3 carbon atoms or a branched, saturated or unsaturated hydrocarbon chain where the main chain is of 1 , 2 or 3 carbon atoms, possibly incorporating an aromatic ring.
  • the surfactant of the invention may be dimeric or oligomeric.
  • the formula of the surfactant is [R-Z] n or [R-X-Y-Z] n , where n is 2-10, preferably 2 or 3.
  • An example of an oligomeric anionic surfactant is oligomerized oleic acid which generally leads to complex mixtures of dimeric and trimeric products.
  • Commercially available oligomers, such as the EmpolTM series of dimmers and trimers are suitable for use in accordance with the present invention.
  • the counter-ion is typically Na + , K + , NH + , or amine salt
  • These mono-, di- or oligomeric carboxylates or sulfonates form viscoelastic aqueous compositions in the presence of salt.
  • the surfactants that are used are biodegrable, more preferably readily biodegradable, when testing using conventional tests such as OECD 306 A-F.
  • Surfactants suitable in the present invention include those known in the art for use in personal care compositions, and include nonionic, anionic, cationic, and amphoteric surfactants.
  • Classes of surfactants useful in personal care compositions, such as personal cleansing compositions, of the present invention include the following: alcohols, alkanolamides, alkylaryl sulfonates, alkylaryl sulfonic acids, alkylbenzenes, amine acetates, amine oxides, amines, sulfonated amines and amides, betaines, block polymers, carboxylated alcohol or alkylphenol ethoxylates, diphenyl sulfonate
  • Anionic surfactants suitable for use in the personal care compositions are the alkyl and alkyl ether sulfates. These materials have the respective formulae- ROSO3M and RO(C 2 H 0)xS0 3 M wherein R is alkyl or alkenyl of from about 8 to about 18 carbon atoms, x is an integer having a value of from 1 to 10, and M is a cation, such as ammonium, alkanolamine such as triethanolamine, monovalent metal, such as sodium or potassium, and polyvalent metal cation, such as magnesium or calcium.
  • the cation M should be selected such that the anionic surfactant component is water soluble. Solubility of the surfactant depends upon the particular anionic surfactants and cations chosen.
  • R has from about 8 to about 18 carbon atoms in both the alkyl and alkyl ether sulfates. In another embodiment, R has from about 10 to about 16 carbon atoms. In even another embodiment, R has from about 12 to about 14 carbon atoms.
  • the alkyl ether sulfates are typically made as condensation products of ethylene oxide and monohydric alcohols having from about 8 to about 24 carbon atoms.
  • the alcohols can be synthetic or they can be derived from fats (e.g., coconut oil, palm kernel oil, tallow). In an embodiment, lauryl alcohol and straight chain alcohols derived from coconut oil or palm kernel oil are preferred.
  • Such alcohols are reacted with between about 0 and about 10, preferably from about 2 to about 5, more preferably about 3, molar proportions of ethylene oxide, and the resulting mixture of molecular species having, for example, an average of 3 moles of ethylene oxide per mole of alcohol, is sulfated and neutralized.
  • alkyl ether sulfates which can be used in the personal care compositions of the present invention include, but are not limited to, sodium and ammonium salts of coconut alkyl triethylene glycol ether sulfate, tallow alkyl triethylene glycol ether sulfate, and tallow alkyl hexaoxyethylene sulfate.
  • alkyl ether sulfates are those comprising a mixture of individual compounds, wherein the compounds in the mixture have an average alkyl chain length of from about 10 to about 16 carbon atoms and an average degree of ethoxylation of from about 1 to about 4 moles of ethylene oxide.
  • Suitable anionic surfactants are the water-soluble salts of organic/sulfuric acid reaction products conforming to the formula- [R 1 ⁇ SO3-M] where R 1 is a straight or branched chain, saturated, aliphatic hydrocarbon radical having from about 8 to about 24, preferably about 10 to about 18, carbon atoms; and M isa cation, such as
  • the cation M should be selected such that the anionic surfactant component is water soluble.
  • Non limiting examples of such surfactants are the salts of an organic sulfuric acid reaction product of a hydrocarbon of the methane series, including iso-, neo-, and n-paraffins, having from about 8 to about 24 carbon atoms, preferably about 12 to about 18 carbon atoms and a sulfonating agent (e.g., SO 3 , H 2 SO 4 ) obtained by known sulfonation methods such as bleaching and hydrolysis.
  • a sulfonating agent e.g., SO 3 , H 2 SO 4
  • alkali metal and ammonium sulfonated C10 to Ci 8 n-paraffins are preferred.
  • Still other suitable anionic surfactants are the reaction products of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil or palm kernel oil; sodium or potassium salts of fatty acid amides of methyl tauride in which the fatty acids, for example, are derived from coconut oil or palm kernel oil.
  • Other similar anionic surfactants are described in U.S. Pat. Nos. 2,486,921 , 2,486,922 and 2,396,278, each of which is incorporated by reference in its entirety herein.
  • Succinates are another type of anionic surfactant suitable for use in the personal care compositions of the present invention. Examples include disodium N- octadecylsulfosuccinnate; disodium lauryl sulfosuccinate; diammonium lauryl
  • sulfosuccinate tetrasodium N-(1 ,2-carboxyethyl)-N-octadecyl sulfosuccinate; diamyl ester of sodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid; and dioctyl esters of sodium sulfosuccinic acid.
  • suitable anionic surfactants include olefin sulfonates having about 10 to about 24 carbon atoms.
  • olefin sulfonates refers to compounds produced by sulfonation of a-olefins by means of uncomplexed sulfur trioxide, followed by neutralization of the acid reaction mixture in conditions such that any sulfones formed in the reaction are hydrolyzed to give the corresponding hydroxy alkane sulfonates.
  • the sulfur trioxide can be liquid or gaseous, and is usually, but not necessarily, diluted by inert diluents (e.g., by liquid SO2, chlorinated hydrocarbons, etc.) when used in the liquid form, or by air, nitrogen, gaseous S0 2 , etc., when used in the gaseous form.
  • a-olefins from which the olefin sulfonates are derived are mono-olefins having from about 10 to about 24 carbon atoms, and preferably from about 12 to about 16 carbon atoms. Preferably, they are straight chain olefins.
  • the olefin sulfonates can contain minor amounts of other materials, such as alkene disulfonates, depending upon reaction conditions, proportion of reactants, nature of the starting olefins and impurities in the olefin stock, and side reactions during the sulfonation process.
  • Combinations of a- olefins are also contemplated for use in the present invention.
  • a non-limiting example of such an a-olefin sulfonate mixture is described in U.S. Pat. No. 3,332,880, which is incorporated by reference in its entirety herein.
  • anionic surfactants suitable for use in the personal care compositions are the ⁇ -alkyloxy alkane sulfonates.
  • suitable anionic surfactants for use in the personal care compositions include ammonium lauryl sulfate, ammonium laureth sulfate, triethylamine lauryl sulfate, triethylamine laureth sulfate, triethanolamine lauryl sulfate, triethanolamine laureth sulfate, monoethanolamine lauryl sulfate,
  • Amphoteric surfactants suitable for use in the personal care composition are well known in the art, and include those surfactants broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be straight or branched chain, wherein at least one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and at least one contains an anionic water solubilizing group such as carboxy, sulfonate, sulfate, phosphate, or phosphonate.
  • Zwitterionic surfactants suitable for use in the personal care composition are well known in the art, and include those surfactants broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds in which the aliphatic radicals are straight or branched chain, and wherein at least one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and at least one contains an anionic group such as carboxy, sulfonate, sulfate, phosphate or phosphonate.
  • Zwitterionic surfactants such as betaines are preferred.
  • Non-limiting examples of other nonionic, anionic, zwitterionic, amphoteric or additional surfactants suitable for use in the personal care compositions are described in
  • Surfactants in the present invention can be used alone or in combination.
  • the hydrophobically modified polymers can be anionic hydrophobically modified polymer or cationic hydrophobically modified polymer or non-ionic hydrophobically modified polymer or zwitterionic hydrophobically modified polymer.
  • the at least one hydrophobically modified polymer is formed from polymerization of ethylenically unsaturated monomers using polymerization conditions known to those skilled in the art.
  • the hydrophobically modified polymers have a number average molecular weight of from 1 ,000, preferably from 1 ,500, for more preferably from 2,500, to 100,000, more preferably to 90,000 and more preferably to 50,000, and even more preferably to 25,000 Da.
  • the polymer molecular weights are as determined with size exclusion chromatography using HPLC grade water comprising 0.025M NaH 2 P0 4 , 0.025 M Na 2 HP0 4 , and 0.01 M of sodium azide which was filtered through a 0.2 ⁇ filter as the eluent and four separation columns, G6000PWxl 7.8 mm x 30 cm, G4000PWxl 7.8 mm x 30 cm, G3000PWxl 7.8 mm x 30 cm, and TSKgel Guard PWxl 6.0 mm x 4 cm as the G2500 Guard column (all ex Tosoh Bioscience).
  • Polyacrylic acid sodium salt standards (ex American Polymer Standards Corporation) were used for calibration. The polymers are prepared in water at a concentration of 0.1 %w/w.
  • the weight average (Mw) and number average molecular weight (Mn) of the standards are:
  • Injection column was 450 ⁇ _ for the standard and sample. Inject the standards and build a first-order or second-order calibration curve. Choose the curve with the best fit and within the range of the sample molecular weight. Run time was 60 minutes per injection for standard and sample.
  • such low molecular weight polymers that in themselves are typically not thickeners, were found to interact with the viscoelastic surfactants in a way that led to an increased viscosity which is much higher than the viscosity of solution of pure viscoelastic surfactant of the same concentration.
  • the hydrophobically-modified polymers of the invention notably its pendant hydrophobic chains, interact in an improved way with the surfactant micelles.
  • the hydrophobically-modified polymer has a backbone and, attached to said backbone, randomly or not, pendant hydrophobic chains.
  • the polymer can be charged or non- charged, depending on the monomers used and the pH of the aqueous composition in which it is used. If too many hydrophobic groups are present, the water-solubility decreases. If it is too low, the interaction with the viscoelastic surfactant will become impaired.
  • the amount of hydrophobic monomer- derived units is about 0.1 mole% or more. In another embodiment it is about 0.5 mole% or more and in a further embodiment it is about 1 mole% or more of all the monomer units comprised in the polymer.
  • the hydrophobically modified polymer comprises monomeric units each covalently bonded to a pendant, optionally alkoxylated, hydrocarbyl group having from 6 to 40 carbon atoms, said pendant, optionally alkoxylated, hydrocarbyl group being connected to the backbone of said hydrophobically modified polymer via a non-ester containing linking group.
  • the pendant, optionally alkoxylated, hydrocarbyl group has from 6, preferably from 8, more preferably from 1 1 , for example from 14, to 40, preferably to 32, more preferred to 24 carbon atoms.
  • the pendant hydrocarbyl group is typically a straight, branched or cyclic, saturated or unsaturated hydrocarbyl, such as a linear or branched alkyl, alkenyl, cycloalkyl, aryl, alkylaryl, alkenylaryl or an alkoxylated derivative thereof.
  • the hydrocarbyl group can optionally be alkoxylated, such as obtained by ethoxylating, propoxylating and/or butoxylating the alcohol or acid corresponding to the hydrocarbyl group.
  • the alkyleneoxy group(s) will be located between the hydrocarbyl group and the polymer backbone.
  • pendant hydrocarbyl groups include behenyl, stearyl, lauryl, 2-etylhexyl, 2-propylheptyl, 2-butyloctyl, 2-hexyldecyl, 2- octyldodecyl, 2-decyltetradecyl, 2-dodecylhexadecyl, 2-tetradecyloctadecyl or their alkoxylated derivatives, or the alkyl group of oleyl, coco, soya, erucyl or tallow acids or alcohols or amines and their alkoxylated derivatives.
  • the carbon atoms in the alkyleneoxy-groups are included in the carbon atom count of the hydrocarbyl group, except for the carbon atoms of any ethyleneoxy- groups, which due to the hydrophilicity of the ethyleneoxy group are not included in the carbon atom count of the hydrocarbyl group.
  • an ethoxylated dodecyl group is an alkoxylated hydrocarbyl group having 12 carbon atoms
  • hexyl propoxylated with 3 propoxylenoxy groups is an alkoxylated hydrocarbyl group having 15 (6 + 9) carbon atoms.
  • the hydrophobically-modified polymer is synthesized by copolymerization of one or more hydrophilic, one or more hydrophobic monomers, and optionally one or more other nonionic monomers.
  • the monomers used can be copolymerized in any sequence.
  • at least acrylic acid is used as a hydrophilic monomer.
  • the hydrophobic monomer is selected from monomers that result in pendant hydrophobic chain, pendant of the backbone of said polymer, having at least 8 carbon atoms in said pendant chain.
  • the amount of hydrophobic monomer-derived units is about 0.1 mole% or more. In another embodiment it is about 0.5 mole% or more and in a further embodiment it is about 1 mole% or more of all the monomer units comprised in the polymer.
  • the pendant, optionally alkoxylated hydrocarbyl group comprises an alkyl function with at most 1 1 carbon atoms and the hydrophobically modified polymer contains, to a level, of from 0.1 , such as from such as from 0.5, for example from 1 , to 20, such as to 10, for example to 5 mole%, based on the amount of monomer units in the polymer, monomeric units connected to such pendant, optionally alkoxylated, hydrocarbyl group.
  • the pendant, optionally alkoxylated hydrocarbyl group is connected to the backbone of the hydrophobically modified polymer by via a non-ester containing linking group.
  • Non- ester containing linking groups may be a direct bond or:
  • f3 ⁇ 4 is a hydrocarbylene group having 1 to 10 carbon atoms, preferably CH 2
  • the top bond of the linking group is connected to the polymer backbone and the bottom bond is connected to the pendant, optionally alkoxylated hydrocarbyl group.
  • the non-ester containing linking group is a, but not limited to, urea, urethane, imide, or amide containing linking group, more preferably a urea or urethane containing linking group.
  • the polymers of the invention can be produced by copolymerizing suitable monomers, as described above, but they can also be produced by modification of a polymer.
  • the polymer is produced in a conventional way by reacting a functional polymer with a hydrophobic modification agent, such as reacting a copolymer of maleic anhydride, including polyisobutylene succinic acid copolymers (PIBSA), with a fatty amine.
  • PIBSA polyisobutylene succinic acid copolymers
  • the hydrophobically modified polymer may be produced by reacting a functional polymer with a hydrophobic modification agent.
  • the hydrophobically modified polymer is suitably free from, or contains at most 1 , preferably at most 0.1 , more preferably at most 0.01 mole% based on the amount of monomer units in the polymer, of monomeric units connected to pendant, optionally alkoxylated, hydrocarbyl group having at least 10, preferably at least 8, more preferably at least 6 carbon atoms connected to the backbone of said hydrophobically modified polymer via an ester containing linking group.
  • the hydrophobically modified polymer may obtained by copolymerizing at least a first and at least a second ethylenically unsaturated monomer, wherein said first monomer is an ethylenically unsaturated monomer with an optionally alkoxylated hydrocarbyl group having from 6, preferably from 8, more preferably from 1 1 to 40, preferably to 32, more preferably to 24 carbon atoms being connected to the unsaturated function of said monomer via a non-ester containing linkage, preferably a urea, urethane, imide and amide containing linkage, more preferably a urea or urethane containing linkage; and said second monomer is an ethylenically unsaturated monomer free from hydrocarbyl groups having at least 1 1 , preferably at least 8, more preferably at least 6 carbon atoms connected to the unsaturated function of the monomer.
  • the first and second monomers are present in a molar ratio of from 0.1 :99.9 to 90:10.
  • the first and second monomers are usually present in a molar ratio of from 0.1 :99.9 to 20:80; preferably from 0.5:99.5 to 10:90, more preferably from 1 :99 to 5:95.
  • the first and second monomers are usually present in a mutual molar ratio of from 1 :99 to 90:10; preferably from 5:95 to 70:30, more preferably from 10:90 to 50:50.
  • the hydrophobically-modified polymer is obtained by first copolymerizing a monomer mixture comprising at least a hydrophobic and a hydrophilic monomer and reacting the resulting copolymer with further hydrophilic or hydrophobic reagents as to refine its properties.
  • Monomers with an optionally alkoxylated hydrocarbyl group having from 6 to 40 carbon atoms connected to the unsaturated function thereof via a non-ester containing linkage include those with the following structure (VI I II I)
  • R is a hydrocarbylene group having from 1 to 10 carbon atoms, preferably CH 2
  • the top bond of X is connected to the double bond in (Villi) and the bottom bond of X is connected to Rh y
  • Rh y is the optionally alkoxylated hydrocarbyl group having from 6, preferably from 8, more preferably form 1 1 to 40, preferably to 32, more preferably to 24 carbon atoms.
  • Hydrophobe-bearing monomers of the above type are commercially available or can be obtained by methods well known in the art, for example by reacting a ethylenically unsaturated isocyanate, such as allyl-isocyanate or 3-isopropyl-benzyl-a,a-dimethyl- isocyanate, with an alcohol or amine containing a hydrocarbyl group (optionally alkoxylated) having from 6 to 40 carbon atoms, by reacting an ethylenically unsaturated acid monomer, such as acrylic acid, with an amine containing a hydrocarbyl group (optionally alkoxylated) having from 6 to 40 carbon atoms.
  • a ethylenically unsaturated isocyanate such as allyl-isocyanate or 3-isopropyl-benzyl-a,a-dimethyl- isocyanate
  • hydrophobe-bearing monomers where the hydrophobe is linked to the double bond of the monomer include t-octyl acrylamide, n-octyl acrylamide, lauryl acrylamide, stearyl acrylamide, behenyl acrylamide, 1 -allyl naphthalene, 2-allyl naphthalene, 1 -vinyl naphthalene, 2-vinyl naphthalene, styrene, a-methyl styrene, 3- methyl styrene, 4-propyl styrene, t-butyl styrene, 4-cyclohexyl styrene, 4-dodecyl styrene, 2-ethyl-4-benzyl styrene and 4-(phenyl butyl) styrene.
  • the ethylenically unsaturated monomer free from hydrocarbyl groups having 1 1 or more, preferably 8 or more, more preferably 6 or more carbon atoms connected to the unsaturated function of the monomer, i.e. the second monomer may be anionic ethylenically unsaturated monomers, cationic ethylenically unsaturated monomers, non- ionically ethylenically unsaturated monomers, zwitterionic ethylenically unsaturated monomers, mixtures thereof and salts thereof.
  • the hydrophobically modified polymer is anionic and is synthesized from at least one first ethylenically unsaturated hydrophobe-bearing monomer and at least one second ethylenically unsaturated monomer that is anionic and referred to as an anionic ethylenically unsaturated monomer hereforth.
  • the hydrophobically modified polymer is cationic and is synthesized from at least one first ethylenically unsaturated hydrophobe-bearing monomer and and at least one second ethylenically unsaturated monomer that is cationic and referred to as a cationic ethylenically unsaturated monomer hereforth.
  • a the hydrophobically modified polymer is non-ionic and is synthesized from at least one first ethylenically unsaturated hydrophobe-bearing monomer and at least one second ethylenically unsaturated monomer that is non-ionic and referred to as a non-ionic ethylenically unsaturated monomer hereforth.
  • a the hydrophobically modified polymer is zwitterionic and is synthesized from at least one first ethylenically unsaturated hydrophobe-bearing monomer and at least one second ethylenically unsaturated monomer that is zwitterionic and referred to as a zwitterionic ethylenically unsaturated monomer hereforth.
  • the polymer contains positive and negative charges which are on the same monomer repeat unit.
  • the hydrophobically modified polymer is zwitterionic and synthesized from at least one first ethylenically unsaturated hydrophobe-bearing monomer and at least one anionic ethylenically unsaturated second monomer and at least one cationic ethylenically unsaturated second monomer and at least one hydrophobe-bearing monomer.
  • the polymer contains positive and negative charges which are on different monomer repeat units.
  • an anionic ethylenically unsaturated monomer is defined as any monomer that is capable of introducing a negative charge to the hydrophobically modified polymer.
  • anionic ethylenically unsaturated monomers include of acrylic acid, methacrylic acid, ethacrylic acid, a-chloro-acrylic acid, a-cyano acrylic acid, /3-methyl-acrylic acid (crotonic acid), a-phenyl acrylic acid, /3-acryloxy propionic acid, sorbic acid, a-chloro sorbic acid, angelic acid, cinnamic acid, p-chloro cinnamic acid, /3-styryl acrylic acid (1 - carboxy-4-phenyl butadiene-1 ,3), itaconic acid, maleic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaric acid, tricarboxy ethylene, 2-acryloxypropionic acid, 2-
  • the preferred salts of hydrophilic acid monomers are sodium, potassium or ammonium salts.
  • Moieties such as maleic anhydride or acrylamide that can be derivatized to an acid- containing group can be used.
  • Combinations of acid-containing hydrophilic monomers can also be used.
  • the acid-containing hydrophilic monomer is acrylic acid, maleic acid, itaconic acid, methacrylic acid, 2-acrylamido-2-methyl propane sulfonic acid , vinyl sulfonic acid, sodium methallyl sulfonate, sulfonated styrene, allyloxybenzene sulfonic acid or mixtures thereof and their salts.
  • Cationic polymers can be obtained by (co)polymerizing a cationic monomer or by functionalizing a polymer after polymerization.
  • Cationic ethylenically unsaturated monomers are ethylenically unsaturated monomers which are capable of introducing a positive charge to the hydrophobically-modified copolymer.
  • the cationic ethylenically unsaturated monomer has at least one amine functionality.
  • the cations in the polymer may be obtained by forming amine salts of all or a portion of the amine functionality, and/or by quaternizing all or a portion of the amine functionality to form quaternary ammonium salts, or by oxidizing all or a portion of the amine functionality to form N-oxide groups.
  • amine salt means that the nitrogen atom of the amine functionality is covalently bonded to from one to three organic groups and from three to one protons, such that there are 4 bonds to the nitrogen and it is associated with an anion.
  • the term "quaternary ammonium salt” means that a nitrogen atom of the amine functionality is covalently bonded to four organic groups and is associated with an anion.
  • Monomers that can form cations include, but are not limited to, N,N-dialkylaminoalkyl (meth)acrylate, N-alkylaminoalkyl (meth)acrylate, N,N-dialkylaminoalkyl (meth)acrylamide and N-alkylaminoalkyl (meth)acrylamide, where the alkyl groups are independently d.-is cyclic compounds such as 1 -vinyl imidazole and the like. Aromatic amine containing monomers such as vinyl pyridine may also be used. Furthermore, monomers such as vinyl formamide, vinyl acetamide and the like which generate amine moieties on hydrolysis may also be used.
  • the cationic ethylenically unsaturated monomer is ⁇ , ⁇ -dimethylaminoethyl methacrylate, tert-butyl aminoethyl methacrylate and ⁇ , ⁇ -dimethylaminopropyl methacrylamide.
  • Cationic ethylenically unsaturated monomers that may be used include the quarternized derivatives of the above monomers as well as diallyldimethylammonium chloride also known as dimethyldiallylammonium chloride, (meth)acrylamidopropyl trimethylammonium chloride, 2-(meth)acryloyloxy ethyl trimethyl ammonium chloride, 2-(meth)acryloyloxy ethyl trimethyl ammonium methyl sulfate, 2-(meth)acryloyloxyethyltrimethyl ammonium chloride, ⁇ , ⁇ -Dimethylaminoethyl (meth)acrylate methyl chloride quaternary, methacryloyloxy ethyl betaine as well as other betaines and sulfobetaines, 2- (meth)acryloyloxy ethyl dimethyl ammonium hydrochloride, 3-(meth)acryloyloxy ethyl dimethyl
  • nonionic ethylenically unsaturated monomer means an ethylenically unsaturated monomer which does not introduce a charge to the hydrophobically-modified copolymer.
  • nonionic ethylenically unsaturated monomers include, but are not limited to, acrylamide, styrene, acylonitrile rmethacrylamide, N-alkyl(meth)acrylamide, N,N-dialkyl(meth)acrylamide such as N,N- dimethylacrylamide, hydroxyalkyl(meth)acrylates, alkyl(meth)acrylates such as, methylacrylate and methylmethacrylate, vinyl acetate, acrylonitrile, vinyl morpholine, vinyl pyrrolidone, vinyl caprolactum, ethoxylated alkyl, alkaryl or aryl monomers such as methoxypolyethylene glycol (meth)acrylate, allyl glycidy
  • non-ionic hydrophobically modified polymer contains vinyl alcohol which is typically generated by hydrolysis of vinyl acetate after the hydrophobically modified polymer has been formed.
  • the nonionic ethylenically unsaturated monomer is preferably water soluble.
  • zwitterionic ethylenically unsaturated monomer means an ethylenically unsaturated monomer which introduces both a positive and a negative charge in the same monomer repeat unit of the hydrophobically modified copolymer.
  • the zwitterionic ethylenically unsaturated monomers include amine oxides carboxybetaine, sulfobetaine, and phosphobetaine monomers. Examples of amine oxides include, but are not limited to, vinyl pyridine-N-oxide and tert-butyl- aminoethylmethacrylate-N-oxide.
  • the monomer say N-vinyl pyridine
  • the monomer can be copolymerized and then the pyridine moiety is oxidized to the amine oxide.
  • carboxybetaine monomers include, but are not limited to, ⁇ , ⁇ '- dimethyl-N-methacryloyloxyethyl-N-(2-carboxyethyl) ammonium, (2-(2-acrylamido-2- methylpropyldimethylammonio) ethanoate, 6-(2-acrylamido-2-methylpropyl dimethyl- ammonio) hexanoate, 4-(N,N-diallyl-N-methylammonio) butanoate, and others.
  • sulfobetaine monomers include, but are not limited to, sulfopropyldimethylammonioethyl methacrylate, sulfoethyldimethylammonioethyl methacrylate, sulfobutyldimethylammonioethyl methacrylate, sulfohydroxy propyl- dimethylammonioethyl methacrylate, sulfopropyldimethyl ammoniopropylacrylamide, sulfopropyldimethylammoniopropylmethacrylamide, sulfohydroxypropyldimethyl- ammoniopropylmethacrylamide, sulfopropyldimethylammonioethyl acrylate, sulfopropyl- diethylammonioethoxyethyl methacrylate, 2-vinyl-l-(3-sulfopropyl) pyridinium betaine,
  • a zwitterionic hydrophobically modified polymer can be synthesized by copolymerizing an anionic ethylenically unsaturated monomer and a cationic ethylenically unsaturated monomer with a hydrophobe-bearing monomer. Any combination of anionic and cationic monomers may be used. However, the preferred anionic monomer will introduce a sulfonate group to the copolymer.
  • a polymer of the present invention may comprise further monomers in addition to those mentioned above.
  • the hydrophobically modified polymers of the invention are not conventional thickeners, due to their low molecular weight.
  • the number average molecular weight of the polymers, neutralized or not may for example be chosen such that they do not thicken a 4 wt% KCI solution in water when used at concentrations of 2 wt% in said KCI solution, at a temperature of 25°C.
  • the molecular weight of the polymer is chosen such that an aqueous solution of 2 wt% of the polymer and 4 wt% of KCI has a viscosity of 100 or less, preferably 50 or less, most preferably 16 mPas or less at a shear rate of 100 sec "1 and a temperature of 25°C.
  • the polymers are neutralized.
  • the polymer overlap concentration c * is a threshold concentration when polymer coils begin to densely pack in a solvent. In a dilute polymer solution where polymer concentration is below c * , the polymer coils are separated. In a polymer solution where the polymer concentration is above c * , the polymer coils are densely packed.
  • c * is measured by the plot of viscosity versus concentration. At low concentrations, the plot will follow a linear path and once the c * is reached, the slope of the line drastically increases.
  • the polymer overlap concentration c * is measured at 25°C at atmospheric pressure in the solvent. Accordingly, in an embodiment it may be desired for economic and environmental reasons to use the polymers of the invention at a polymer concentration that is below the overlap concentration c * .
  • polymers of the invention were found to interact with viscoelastic surfactants in such a way that the combined use leads to increased viscosities at high temperature (tested up to 100°C) and pressures (tested up to 25 bara.)
  • the combination of viscoelastic surfactant and polymer of the invention is supplied in a concentrated form, it is preferably in an aqueous, essentially salt-free form.
  • an aqueous concentrate has the advantage of having a low viscosity and related easy dilution.
  • Typical aqueous concentrates comprise one or more glycols, such as propylene glycol, so that the viscoelastic surfactant is more easily dissolved in the concentrate.
  • the amount of viscoelastic surfactant in such a concentrate is within the range of greater than 10 %w/w, preferably 10-60 %w/w, whereas the amount of polymer ranges from about 5-30 %w/w, based on the weight of the concentrate.
  • essentially salt-free it is meant that the salt concentration is less than 0.01 %w/w, otherwise the viscosity becomes unacceptably high.
  • the viscoelastic surfactant is used in an amount below about 40 %w/w, preferentially, below about 20 %w/w of the final viscoelastic aqueous composition. Also the viscoelastic surfactant is suitably used in an amount of about 1 %w/w or more. In an embodiment it is about 5 %w/w or more, while in another embodiment it is about 7%w/w or more, all being based on the weight of the total viscoelastic aqueous composition.
  • the hydrophobically modified polymer is used in an amount of 10 %w/w or less. In an embodiment of the invention, it is 5 %w/w or less. In another embodiment it is 2% or less, while in a further embodiment it is 1 %w/w or less.
  • the polymer is to be used in an amount of at least 0.01 %w/w. All of these amounts are based on the weight of the total viscoelastic aqueous composition.
  • the weight ratio of hydrophobically modified polymer to viscoelastic surfactant is usually from 0.1 :100, preferably from 1 :100, more preferably from 3:100, to 100:50, preferably to 100:100, more preferably to 50:100.
  • the viscoelastic compositions of the invention may also comprise one or more chelating agents. Particularly when the aqueous formulations or the area where the compositions are used has a lot of hardness ions, the use of chelating agents for such ions was found to be beneficial. Without wishing to be bound by theory, it is thought that these hardness ions tend to precipitate the hydrophobically modified polymer in the aqueous solution.
  • chelating agents prevents the precipitation of these hydrophobically modified polymers and preserves the performance of the mixture of these polymers and viscoelastic surfactants in high hardness aqueous solutions.
  • a chelating agent is described as any material that will chelate hardness ions, such as calcium and magnesium, in aqueous solutions.
  • Chelating agents include but are not limited to (S,S)-ethylenediaminesuccinic acid trisodium salt, N,N-bis(carboxymethyl)-L-glutamic acid tetrasodium salt, L-aspartate- (N,N)-diacetic acid tetrasodium salt, N-2-hydroxyethyliminodiacetic acid disodium salt, methylglycinediacetic acid trisodium salt, ethylenediaminetetraacetic acid, nitorilotriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid, triethylenetetraminehexaacetic acid, 1 ,3- propanediaminetetraacetic acid, 1 ,3-diamino-2-hydroxypropanetetraacetic acid, dihydroxyethylglycine, glycol ether diamine tetraacetic acid, hydroxyethanediphosphonic acid, amino
  • the preferred chelating agents are aminocarboxylates, such as (S,S)-ethylenediaminesuccinic acid trisodium salt, N,N- bis(carboxymethyl)-L-glutamic acid tetrasodium salt, L-aspartate-(N,N)-diacetic acid tetrasodium salt, N-2-hydroxyethyliminodiacetic acid disodium salt, methylglycinediacetic acid trisodium salt, ethylenediaminetetraacetic acid, nitrilotriacetic acid, and their salts.
  • aminocarboxylates such as (S,S)-ethylenediaminesuccinic acid trisodium salt, N,N- bis(carboxymethyl)-L-glutamic acid tetrasodium salt, L-aspartate-(N,N)-diacetic acid tetrasodium salt, N-2-hydroxyethyliminodiacetic acid disodium
  • a high hardness aqueous solution is defined as a solution with a hardness of greater than 100 ppm expressed as CaC0 3 , more preferably greater than 250 ppm as CaC0 3 , and most preferably greater than 500 ppm as CaC0 3 .
  • the personal care compositions of the present invention also include a personal care active ingredient.
  • a personal care active ingredient in hair care
  • the personal care active ingredients may provide beneficial properties to hair such as improved cleanliness, fragrance, improved shine, improved wet combability, improved dry combability, improved wet feel, improved dry feel, improved strength, or improved color.
  • the personal care active ingredients may provide beneficial properties to skin such as improved cleanliness, fragrance,
  • Such active ingredients include, without limitation, thickeners, emulsifiers, aesthetic modifiers, UV filters, humectants (such as
  • the personal care composition may be a hair care formulation, such as a shampoo or a conditioner, or a skin care formulation such as a body wash or shave preparation.
  • the active ingredient will be present in the personal care composition from about 0.01 to about 10% of the total formula weight. In an embodiment of this invention the active ingredient will be present from about 0.1 to about 5 percent by weight based on the total weight of the personal care formulation (dry basis). In another embodiment, the active viscoelastic aqueous composition will be present from about 0.3 to 4% of the total weight of personal care formulation (dry basis).
  • the viscoelastic aqueous composition will be present from about 0.1 to about 10wt% of the total personal care formulation (dry basis). In an embodiment of this invention the viscoelastic aqueous composition will be present from about 0.2 to about 5wt% of the total personal care formulation (dry basis). In another embodiment, the viscoelastic aqueous composition will be present from about 0.3 to 4wt% of the total weight of the personal care formulation (dry basis).
  • salt can be added to the formulation to assist in increasing viscosity.
  • Typical levels of salt that can be added to the personal care composition will be from about 0.1 to about 10% based on the total weight of the composition.
  • Typical salts will be, for example, alkaline metal and alkaline earth cations of common anions (e.g.
  • the salt will be sodium chloride, calcium chloride or mixtures thereof. In yet another embodiment the salt will be present in an amount from about 1 to about 5 percent based on the total weight of the composition.
  • the viscosity of samples has been determined over a broad shear rate range using a stress-controlled rheometer SR-5000 (from Rheometric Scientific, which is now TA Instruments).
  • the sample was placed between two circular parallel plates of 25 mm or 40 mm in diameter and evaluated at a temperature of 25 °C.
  • the initial stress was 0.5 Pa and the final stress was in the 150-400 Pa range, depending on the viscosity of the sample, with the lower final stress selected for samples with lower viscosity.
  • Aromox® APA-TW is a commercial tallowalkylamidopropyl dimethyl amine oxide supplied by AkzoNobel.
  • POLYFLOS ® HM 21 is a hydrophobically modified hydroxypropyl guar gum supplied by Lamberti spa, and was used as received. This polymer was used as a comparison for the polymers of the invention.
  • a scavenge feed (to minimize residual monomer) containing 0.175 g of sodium persulfate dissolved in 10 g of water was then added to the reactor over 30 minutes and maintained for an additional 30 minutes.
  • the reactor was then set up for distillation which was carried out at increased temperature and/or reduced pressure, to ensure a controlled distillation without polymer degradation.
  • a small amount of ANTIFOAM® 1400 (0.12 g) (from Dow Chemical) was added to suppress any foam generated during distillation.
  • the alcohol (the cosolvent) was removed from the polymer solution by azeotropic distillation. During the distillation, about 1350 g of water was added. Approximately, 263 g of a mixture of water and isopropyl alcohol were distilled off. After distillation was completed, the reaction mixture was cooled and 21.8 g of 50% NaOH was added. The final product had a pH of 2.2 and solids of 13.3 percent.
  • a scavenge feed containing 0.17 g of sodium persulfate dissolved in 10 g of water was then added to the reactor over 30 minutes and held at temperature for an additional 30 minutes.
  • the reactor was then set up for distillation.
  • a small amount of ANTIFOAM® 1400 (0.12 g) (from Dow Chemical) was added to suppress any foam generated during distillation.
  • the alcohol cosolvent was removed from the polymer solution by azeotropic distillation. During the distillation, about 1080 g of water was added. Approximately, 251 g of a mixture of water and isopropyl alcohol were distilled off. After distillation was completed, the reaction mixture was cooled. The final product had a pH of 2.5 and solids of 15.7 percent.
  • An initiator solution of 0.97 g of sodium persulfate dissolved in 28.3 g of water was simultaneously added but over a period of 90 minutes.
  • the reaction temperature was maintained at about 85°C for one hour.
  • a scavenge feed containing 0.15 g of sodium persulfate dissolved in 10 g of water was then added to the reactor over 30 minutes and the temperature was held for an additional 30 minutes.
  • the reactor was then set up for distillation and a small amount of ANTIFOAM® 1400 (0.12 g) (from Dow Chemical) was added to suppress any foam generated during distillation.
  • the alcohol cosolvent was removed from the polymer solution by azeotropic distillation. Approximately, 185 g of a mixture of water and isopropyl alcohol were distilled off.
  • Preparation of polymer R7 -33-158 An initial charge of 77 g of water and 100 g of isopropanol were added to a 1 liter glass reactor. The reactor contents were heated to 82°C. A first solution which is a mixture of 72.7 g of acrylic acid and 21.6 g of an N-octadecyl acrylamide dissolved in 50 g of isopropanol was added to the reactor over a period of 80 minutes. A second solution of 0.97 g of sodium persulfate dissolved in 46 g of water was simultaneously added at the same time but over a period of 90 minutes.
  • Table 1 Analysis of the hydrophobically modified polymers compared with the conventional POLYFLOS ® HM 21.
  • Example 1 and Comparative examples A-B Rheology of Aromox APA-TW and hydrophobically modified polymer R7-33-43
  • a strain-controlled rheometer ARES (from Rheometric Scientific, which is now TA Instruments) was used to conduct the Steady Strain Rate Sweep at 25°C, with an initial strain rate of 0.01 s "1 and a final strain rate of 100 s ⁇ 1 . Data was collected, 10 data points per strain rate decade. Parallel plates of diameter of 25 mm were used, and temperature was controlled by peltier heating.
  • the rheology profile is graphed in Figure 1 .
  • Clearly sample 1 shows significantly higher viscosity than sample A and sample B, indicating a synergistic viscosity increase achieved by combination of Aromox APA-TW and R7-33-43 polymer (a polymer with a urethane linkage) in 4% KCI. The same synergistic viscosity increase was also found at 50°C and at 80°C.
  • a strain-controlled rheometer ARES (from Rheometric Scientific, which is now TA Instruments) was used to conduct the Steady Strain Rate Sweep at 25°C, with an initial strain rate of 0.01 s "1 and a final strain rate of 100 s ⁇ 1 . Data was collected, 10 data points per strain rate decade. Parallel plates of diameter of 25 mm were used, and temperature was controlled by peltier heating.
  • the rheology profile is graphed in Figure 2. Again, sample 2 shows significantly higher viscosity than sample C and sample D, indicating a synergistic viscosity increase achieved by combination of Aromox APA-TW and R7-33-61 polymer (a polymer with a urea linkage) in 4% KCI. The same synergistic viscosity increase was also found at 50°C and at 80°C
  • Comparative examples E and F Rheology of Aromox® APA-TW and POLYFLOS® HM 21 . Formulations were as shown in Table 4. Table 4: Sample Preparation of Aromox APA-TW + POLYFLOS ® HM 21
  • Example 5 In these examples the experiment of Example 5 was repeated, except that hydrophobically modified polymer R7 -33-43 was used, while also using the well-known chelate EDTA (Dissolvine NA) in the composition. Samples 6 and J were prepared according to the amount shown in Table 7.
  • Figure 5 shows the viscosity of these formulations. The results show that the combination of viscoelastic surfactant and low molecular weight hydrophobically modified polymer gives exceptionally high viscosity at low concentrations also in the presence of a chelate.
  • a strain-controlled rheometer ARES (from Rheometric Scientific, which is now TA Instruments) was used to conduct the Steady Strain Rate Sweep at 25°C, with an initial strain rate of 0.01 s "1 and a final strain rate of 100 s ⁇ 1 . Data was collected, 10 data points per strain rate decade. Parallel plates of diameter of 25 mm were used, and temperature was controlled by peltier heating. Figure 6 shows the viscosity of these samples. One can see from the overlap rheology profiles that the viscosity of sample 7 is higher than that of sample K in the shear rate range tested.
  • the blend of Aromox APA-TW and polymer R7-33-158 (a polymer with an amide linkage between the pendant hydrophobe and the backbone) has higher viscosity than Aromox APA-TW alone.
  • a strain-controlled rheometer ARES (from Rheometric Scientific, which is now TA Instruments) was used to conduct the Steady Strain Rate Sweep at 25°C, with an initial strain rate of 0.01 s "1 and a final strain rate of 100 s ⁇ 1 . Data was collected, 10 data points per strain rate decade. Parallel plates of diameter of 25 mm were used, and temperature was controlled by peltier heating.
  • Figure 7 shows the viscosity of these samples.
  • Aromox APA-TW and polymer R7-33-28 (a polymer with an ester linkage between the pendant hydrophobe and the backbone) has lower viscosity than Aromox APA-TW alone.
  • blending VES and polymer showed a "negative" rheology synergy.
  • Samples 8 and N was prepared according to the amounts indicated in the following Table 10. Table 10 - preparation of samples 8 and N
  • Sample N had no polymer, and its phase angle is mostly higher than 45 degrees. Its phase angle was only below 45 degrees at frequency higher than 3 rad/s, indicating that it only has viscoelastic characteristics at frequencies higher than 3 rad/s.
  • Sample 8 was the blend of Aromox APA-TW and polymer R7-33-43, and its phase angle was below 45 degrees at frequencies higher than 0.02 rad/s. This is another data to support that the VES-polymer blend is more viscoelastic than VES alone.
  • a strain-controlled rheometer ARES (from Rheometric Scientific, which is now TA Instruments) was used to conduct the Steady Strain Rate Sweep at 25°C, with an initial strain rate of 0.01 s "1 and a final strain rate of 100 s ⁇ 1 . Data was collected, 10 data points per strain rate decade. Parallel plates of diameter of 25 mm were used, and temperature was controlled by peltier heating.
  • Figure 10 shows the results from these experiments.
  • a strain-controlled rheometer ARES from Rheometrics, which is now TA Instrument
  • ARES Steady Strain Rate Sweep at 25°C
  • Parallel plates of diameter of 25 mm were used, and temperature was controlled by peltier heating.
  • a stress-controlled rheometer SR-5000 (from Rheometrics, which is now TA Instrument) was used to conduct the Steady Stress Sweep at 25°C, with an initial stress of 0.1 Pa, a final stress of 40 Pa, and a linear stress increment of 0.5 Pa.
  • Parallel plates of diameter of 40 mm were used, and temperature was controlled by peltier heating.
  • Sodium lauryl ether sulfate and cocamidopropyl betaine were chosen as exemplary surfactants. They were used in a constant ratio to each other of 4:1 respectively.
  • a series of eight dilution experiments were conducted. The compositions of the two series of experiments are found in Table 12 shown below.
  • Sodium Chloride was the salt used in all the samples in Example 10.
  • the first four dilution experiments (labeled 1 -4) represent "no polymer controls".
  • the latter four dilution experiments (labeled 5-8) contain different levels of a polymer R7-36-72 of the current invention.
  • Columns A-D represent fixed levels of surfactant (column A for 15% surfactant, B for 10% surfactant, C for 7.5% surfactant, and D for 6% surfactant).
  • Table 13 the zero shear viscosities are shown to correlate with the dilution experiments described in Table 12.
  • Zero shear viscosities were obtained from either a plot of viscosity vs. shear rate or fitting the data to Cross model. Viscosities were measured using a stress-controlled rheometer SR-5000 (from Rheometric Scientific, which is now TA lnstruments)a stress controlled rheometer utilizing a 25 mm diameter parallel plate configuration and 1 mm gap. Steady state stress sweep measurements were carried out at 25 °C a data at different shear rate were obtained.
  • R7 -36-72 can effectively increase the zero shear viscosity for the sodium lauryl ether sulfate/cocamidopropyl betaine mixture over all surfactant levels to levels higher than can be achieved without polymer. Additionally, it can generally be seen that the peak viscosity of the system can be achieved with lower salt levels than in the absence of the polymer of the present invention. Furthermore, it can be observed that the zero shear viscosity of a high surfactant containing system can be achieved at substantially lower surfactant content by the addition of the polymer of the present invention with the appropriate level of salt.
  • Peak viscosity refers to the highest viscosity achieved over the entire salt range that was tested. Table 14
  • Dynamic stress sweep were also evaluated using the Rheometric Scientific rheometer and same plate configuration as for steady state stress sweep. Measurement was carried out at a frequency of 1 Hz. These values allow us to investigate yield stress, storage (elastic) and loss (viscous) modulus. Figure below shows a typical example.
  • Composition 1 containing 7.5% of surfactant, 3% Sodium Chloride, and 0% polymer was prepared and evaluated according to Example 10.
  • Composition 2 containing 7.5% surfactant, 3% Sodium Chloride, and 0.2% R7-36-72 was prepared and evaluated according to Example 5.
  • Foam property was evaluated by creating a foam using a blender and the measuring the time taken for half of total liquid to drain from the foam matrix.

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WO2012080382A1 (en) 2012-06-21
WO2012080383A2 (en) 2012-06-21
US9080043B2 (en) 2015-07-14
JP2014502602A (ja) 2014-02-03
EA025071B1 (ru) 2016-11-30
AU2011343287B2 (en) 2015-07-30
US20130274170A1 (en) 2013-10-17
EP2652075B1 (de) 2015-06-24
BR112013014234B1 (pt) 2021-06-22
US20130266531A1 (en) 2013-10-10
EP2652072A1 (de) 2013-10-23
AU2011343287A1 (en) 2013-07-25
CN103648589A (zh) 2014-03-19
BR112013014231A2 (pt) 2016-07-12
WO2012080383A3 (en) 2013-09-26
CN103261365A (zh) 2013-08-21
EA201390807A1 (ru) 2013-11-29
EP2940095A1 (de) 2015-11-04
CA2819565C (en) 2020-07-21
BR112013014234A2 (pt) 2016-09-13
CA2819565A1 (en) 2012-06-21

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